Diamond, atomic structure

Fig. 16.3. Covalent ceramics, (a) The diamond-cubic structure each atom bonds to four neighbours.

Silicon atoms bond strongly with four oxygen atoms to give a tetrahedral unit (Fig. 16.4a). This stable tetrahedron is the basic unit in all silicates, including that of pure silica (Fig. 16.3c) note that it is just the diamond cubic structure with every C atom replaced by an Si04 unit. But there are a number of other, quite different, ways in which the tetrahedra can be linked together. 

Pure silica contains no metal ions and every oxygen becomes a bridge between two silicon atoms giving a three-dimensional network. The high-temperature form, shown in Fig. 16.3(c), is cubic the tetrahedra are stacked in the same way as the carbon atoms in the diamond-cubic structure. At room temperature the stable crystalline form of silica is more complicated but, as before, it is a three-dimensional network in which all the oxygens bridge silicons. 

Later, the name diamondoids was chosen for all the higher cage hydrocarbon compounds of this series because they have the same structure as the diamond lattice highly symmetrical and strain-free so that their carbon atom structure can be superimposed on a diamond lattice, as shown in Fig. 5 for adamantane, diamantane, and triamantane. These compounds are also known as adamanto-logs and polymantanes. 

The work on carbon nitride solids is strongly related to research on diamondlike carbon (DLC) materials [5, 6]. DLC materials are thin film amorphous metastable carbon-based solids, pure or alloyed with hydrogen, which have properties similar to that of crystalline diamond (high hardness, low friction coefficient, high resistance to wear and chemical attack). This resemblance to diamond is due to the DLC structure, which is characterized by a high fraction of highly cross-linked sp -hybridized carbon atoms. To obtain this diamond-like structure... 

Figure 4.2 Quasi-hexagonal dislocation loop lying on the (111) glide plane of the diamond crystal structure. The <110> Burgers vector is indicated. A segment, displaced by one atomic plane, with a pair of kinks, is shown a the right-hand screw orientation of the loop. As the kinks move apart along the screw dislocation, more of it moves to the right.

Figure 11.1 Comparison of the atomic structure of cristobalite (high temperature form of Si02) with that of silicon (diamond structure using tetrahedral unit cell).

Natural diamond Natural graphite Synthetic diamond alloyed with iron, 23 248 in amorphous silica, 22 385 antimony impregnated, 3 53 atomic structure of, 22 232 biologically active, 17 803 as a blast furnace refractory,... 

Sphalerite and wurtzite structures general remarks. Compounds isostructural with the cubic cF8-ZnS sphalerite include AgSe, A1P, AlAs, AlSb, BAs, GaAs, InAs, BeS, BeSe, BeTe, BePo, CdS, CdSe, CdTe, CdPo, HgS, HgSe, HgTe, etc. The sphalerite structure can be described as a derivative structure of the diamond-type structure. Alternatively, we may describe the same structure as a derivative of the cubic close-packed structure (cF4-Cu type) in which a set of tetrahedral holes has been filled-in. This alternative description would be especially convenient when the atomic diameter ratio of the two species is close to 0.225 see the comments reported in 3.7.3.1. In a similar way the closely related hP4-ZnO... 

Dawson and coworkers pioneered the application of the OPP model to diamond-type structures (Dawson 1967, Dawson et al. 1967). In the diamond-type structure, common to diamond, silicon, and germanium, the atoms are located at 1/8, 1/8, 1/8, at the center-of-symmetry related position at —1/8, —1/8, —1/8, and repeated in a face-centered arrangement. The tetrahedral symmetry of the atomic sites greatly limits the allowed coefficients in the expansion of Eq. (2.39). With x, y, z expressed relative to the nuclear position, the potential is given by... 

As first shown by Dawson (1967), Eq. (11.3) can be generalized by inclusion of anharmonicity of the thermal motion, which becomes pronounced at higher temperatures. We express the anharmonic temperature factor of the diamond-type structure [Chapter 2, Eq. (2.45)] as 71(H) = TC(H) -f iX(H), in analogy with the description of the atomic scattering factors. Incorporation of the temperature... 

A large number of binary AB compounds formed by elements of groups IIIA and VA or IIA and VIA (the so-called III-V and II-VI compounds) also fcrystallize in diamond-like structures. Among the I-VII compounds, copper (I) halides and Agl crystallize in this structure. Unlike in diamond, the bonds in such binary compounds are not entirely covalent because of the difference in electronegativity between the constituent atoms. This can be understood in terms of the fractional ionic character or ionicity of bonds in these crystals. 

On the other hand, in covalently bonded materials like carbon, silicon, and germanium, the formation of energy bands first involves the hybridization of the outer s- and p-orbitals to form four identical orbitals, ilnh, which form an angle of 109.5° with each other, that is, each C, Si, and Ge atom is tetrahedrally coordinated with the other C, Si, and Ge atom, respectively (Figure 1.16), resulting in a diamond-type structure. 

FIGURE 1.16 Tetrahedral bonding of atoms in a diamond-type structure of C, Si, and Ge crystals. 

This section presents a brief overview of a few other compounds that have not been described in previous sections. Because it can function as a nonmetal, silicon forms sihcides with several metals. These materials are often considered as alloys in which the metal and silicon atoms surround each other in a pattern that may lead to unusual stoichiometry. Examples of this type are Mo3Si and TiSi2. In some sihcides, the Si-Si distance is about 235 pm, a distance that is quite close to the value of 234 pm found in the diamond-type structure of elemental silicon. This indicates that the structure contains Si22-, and CaSi2 is a compound of this type. This compound is analogous to calcium carbide, CaC2 (actually an acetylide that contains C22- ions (see Chapter 10)). 

Diamondoid A material with a superior strength-to-weight ratio (100 to 250 times as strong as titanium) but much lighter. These diamond-like structures contain dense, three-dimensional networks of covalent bonds, formed mostly from first- and second-row atoms with a valence of three or more. 

Sawyer L, Shotton DM, Campbell JW, Wendell PL, Muirhead H, Watson HC, Diamond R, Ladner RC (1978) The atomic structure of crystalline porcine pancreatic elastase at 2.5 A resolution Comparison with the structure of a-chymotrypsin. J Mol Biol 118 137-208... 

Silicon and germanium are the most important elemental semiconductors. They have the diamond cubic structure with sp hybrid bonds. The structure of the low index crystallographic planes, the only ones to be considered here, is shown in Fig. 1. It is seen that in the ill surfaces the atoms are triply bonded to the layer below and thus have one unpaired electron (dangling bond). Each atom of the 110 surfaces also... 

To date, inorganic materials have been used in most semiconductor applications. The most studied and technologically important inorganic semiconductors have the diamond (e.g.. Si) or zinc-blende (e.g., Ga As) crystal structure. Figure 1 shows the zinc-blende crystal structure and the corresponding BrOouin zone. (The symbols label special symmetry points in the zone.) The structure is based on an fee lattice with two atoms per unit cell. The diamond crystal structure is the same as the zinc-blende structure, except that the two atoms in the unit cell are the same for diamond, whereas they are different for zinc blende. The Brillouin zones are the same for the two structures, but for the diamond structure, there is an additional inversion symmetry operator. 

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